Single-atom (SA) cocatalysts (SACs) have garnered significant attention in photocatalysis due to their unique electronic properties and high atom utilization efficiency. This review provides an overview of the concept and principles of SA cocatalyst in photocatalysis, emphasizing the intrinsic differences to SAs used in classic chemical catalysis. Key factors that influence the efficiency of SAs in photocatalytic reactions, particularly in photocatalytic hydrogen (H2) production, are highlighted. This review further covers synthesis methods, stabilization strategies, and characterization techniques for common SAs used in photocatalysis. Notably, "reactive deposition" method, which often shows a self-homing effect and thus achieves a maximum utilization efficiency of SA cocatalysts, is emphasized. Furthermore, the applications of SA cocatalysts in various photocatalytic processes, including H2 evolution, carbon dioxide reduction, nitrogen fixation, and organic synthesis, are comprehensively reviewed, along with insights into common artifacts in these applications. This review concludes by addressing the challenges faced by SACs in photocatalysis and offering perspectives on future developments, with the aim of informing and advancing research on SAs for photocatalytic energy conversion.

• Keywords
• cocatalyst, hydrogen production, photocatalysis, single atom,
• Publication type
• Journal Article MeSH
• Review MeSH

Titanium dioxide (TiO2 ) and, in particular, its anatase polymorph, is widely studied for photocatalytic H2 production. In the present work, we examine the importance of reactive facets of anatase crystallites on the photocatalytic H2 evolution from aqueous methanol solutions. For this, we synthesized anatase TiO2 nanocrystals with a large amount of either {001} facets, that is, nanosheets, or {101} facets, that is, octahedral nanocubes, and examined their photocatalytic H2 evolution and then repeated this procedure with samples where Pt co-catalyst is present on all facets. Octahedral nanocubes with abundant {101} facets produce >4 times more H2 than nanosheets enriched in {001} facets if the reaction is carried out under co-catalyst-free conditions. For samples that carry Pt co-catalyst on both {001} and {101} facets, faceting loses entirely its significance. This demonstrates that the beneficial role of faceting, namely the introduction of {101} facets that act as electron transfer mediator is relevant only for co-catalyst-free TiO2 surfaces.

• Keywords
• Pt co-catalyst, anatase TiO2, crystal facet engineering, photocatalytic H2 evolution,
• Publication type
• Journal Article MeSH